U.S. patent number 5,424,438 [Application Number 08/178,040] was granted by the patent office on 1995-06-13 for polishes for metal surfaces containing cationic emulsifiers, and cationic emulsifiers contained therein.
This patent grant is currently assigned to Ausimont S.p.A.. Invention is credited to Viviana Boselli, Alba Chittofrati, Giovanni Gavazzi, Renato Spiti, Ezio Strepparola, Silvia Tresoldi.
United States Patent |
5,424,438 |
Chittofrati , et
al. |
June 13, 1995 |
**Please see images for:
( Certificate of Correction ) ** |
Polishes for metal surfaces containing cationic emulsifiers, and
cationic emulsifiers contained therein
Abstract
Polishes for metal surfaces, based on dispersions of waxes,
fluorinated polymers and perfluoropolyoxyalkylene oils acquire high
gloss characteristics combined with improved water-repellency and
resistance to soiling of 0.1-5% by weight of at least a cationic
emulsifier comprised in the general formula where: R=a chain of
perfluoropolyoxyalkylene units; L=a divalent organic group; Q=a
polar group; X=a halogen, or a group of formula
R"=F-(CF.sub.2).sub.m -; t=1 or 2; m=1-4. The polished containing
the emulsifiers of formula (I) as well as the compounds comprised
in said formula are claimed as new products.
Inventors: |
Chittofrati; Alba (Milan,
IT), Boselli; Viviana (Milan, IT), Gavazzi;
Giovanni (Cassano d'Adda, IT), Strepparola; Ezio
(Treviglio, IT), Spiti; Renato (Sesto San Giovanni,
IT), Tresoldi; Silvia (Cornate d'Adda,
IT) |
Assignee: |
Ausimont S.p.A.
(IT)
|
Family
ID: |
11362040 |
Appl.
No.: |
08/178,040 |
Filed: |
January 6, 1994 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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20144 |
Feb 19, 1993 |
5294248 |
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Foreign Application Priority Data
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Feb 20, 1992 [IT] |
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MI92A0360 |
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Current U.S.
Class: |
546/336; 546/339;
560/125; 546/133; 546/341; 546/340; 560/159; 544/168; 568/11;
564/294; 564/292; 560/155 |
Current CPC
Class: |
C09G
1/10 (20130101); C08G 65/007 (20130101) |
Current International
Class: |
C09G
1/10 (20060101); C09G 1/00 (20060101); C08G
65/00 (20060101); C07D 213/60 () |
Field of
Search: |
;546/339,340,341,336
;568/11,12,9 ;564/503,505,292,294 ;560/555,575 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Yokoji, Toraichi "Glazing Wax", Chemical Abstracts, vol. 87,
Abstract No. 186202s (1967)..
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Primary Examiner: Reamer; James H.
Attorney, Agent or Firm: Cave; Bryan
Parent Case Text
This is a divisional, of U.S. Application Ser. No. 08/020,144,
filed Feb. 19, 1993 now U.S. Pat. No. 5,294,248.
Claims
We claim:
1. Compounds having the formula ##STR10## in which: R is a
perfluoropolyoxyalkylene chain having an average molecular weight
ranging from 400 to 2000 which comprises perfluorooxyalkylene units
having at least one of the following structures: ##STR11## L is a
divalent organic group selected from the group consisting of:
-CH.sub.2 O-C (=O)-CH.sub.2 -
-CH.sub.2 O-(CH.sub.2 -CH.sub.2 O).sub.n,-CH.sub.2 -CH.sub.2 -,
-CH.sub.2 O-(CH.sub.2 -CH.sub.2 O).sub.n,-C(=O)-CH.sub.2 -, and
-C(=O) -N(R')-(-CH.sub.2).sub.n,-CH.sub.2 -
wherein
n' is an integer from 1 to 3; and
R' is hydrogen or a C.sub.1 -C.sub.4 alkyl group;
t is an integer from 1 to 2;
Q is a polar organic group comprising N or P atoms as positive
charge carriers, and having the formula: ##STR12## wherein A.sup.+
is
i) a N or a P atom and R.sub.1, R.sub.2, and R.sub.3 are
independently an alkyl group having from 1 to 12 carbon atoms,
or
ii) a P atom and R.sub.1, R.sub.2, and R.sub.3 are independently an
alkyl group having from 1 to 12 carbon atoms, or an aryl group,
or
Q is an aromatic ring, a saturated aliphatic ring, or an
unsaturated aliphatic ring, wherein said aromatic or aliphatic
rings have in the ring N or P atoms as a positive charge carrier
bound to group L; and
X.sup.- is an anion.
2. The compounds of claim 1, wherein X.sup.- is selected from the
group consisting of: halogen; acetate; CH.sub.3 -phenylene-SO.sub.3
-; and R"SO.sub.3 -, wherein R"=F(CF.sub.2).sub.m -, and m=a number
from 1 to 4.
3. The compounds of claim 1, wherein the average molecular weight
of R ranges from 500 to 1,000.
4. A compound according to claim 1 wherein the
perfluoropolyoxyalkylene chain R is: ##STR13## wherein Rf is a
C.sub.1 -C.sub.3 alkyl group, either thoroughly fluorinated or
thoroughly fluorinated except for being substituted by an atom of
hydrogen or chlorine besides fluorine;
R'f is a -CF.sub.2 - or a ##STR14## and m, n, and p are each such
numbers as to impart to R a molecular weight from 400 to 2000.
5. A compound according to claim 1 wherein
1) t is 1 and the perfluoropolyoxyalkylene chain R is:
wherein
Rf is a -CF.sub.3 or -CF.sub.2 -CF.sub.3 group,
Rf' is a -CF.sub.2 group, and
m and n are each such numbers as to impart to R a molecular weight
from 400 to 2000, or
2) t is 2 and the perfluoropolyoxyalkylene chain R is:
wherein
Rf and Rf are each a -CF.sub.2 - group, and
m and n are each such numbers as to impart to R a molecular weight
from 400 to 2000.
6. A compound according to claim 1 wherein the
perfluoropolyoxyalkylene chain R is: ##STR15## wherein Rf is a
C.sub.1 -C.sub.3 alkyl group, either thoroughly fluorinated or
thoroughly fluorinated except for being substituted by an atom of
hydrogen or chlorine besides fluorine;
R'f is a -CF.sub.2 - or a ##STR16## and m, n, p and q are each such
numbers as to impart to R a molecular weight from 400 to 2000.
7. A compound according to claim 1 wherein the
perfluoropolyoxyalkylene chain R is: ##STR17## wherein Rf is
-CF.sub.2 -CF.sub.2 -CF.sub.3 group, Rf' is a ##STR18## and n is
such a number as to impart to R a molecular weight from 400 to
2000.
8. A compound according to claim 1 wherein the
perfluoropolyoxyalkylene chain R is:
wherein
Rf is -CF.sub.3 or -CF.sub.2 -CF.sub.3 group, Rf' is a -CF.sub.2
group, and and n is such a number as to impart to R a molecular
weight from 400 to 2000.
9. A compound according to claim 1 wherein the
perfluoropolyoxyalkylene chain R is:
wherein
Rf is -CF.sub.3 or -CF.sub.2 -CF.sub.3 group, Rf' is a -CF.sub.2
-CF.sub.2 - group, and n is such a number as to impart to R a
molecular weight from 400 to 2000.
10. Compounds having the formula
in which:
R is a perfluoropolyoxyalkylene chain having an average molecular
weight ranging from 400 to 2000 which comprises
perfluorooxyalkylene units having at least one of the following
structures: ##STR19## L is a divalent organic group selected from
the group consisting of: -CH.sub.2 O-C(=O)-CH.sub.2 -
-CH.sub.2 O-(CH.sub.2 -CH.sub.2 O).sub.n,-CH.sub.2 -CH.sub.2 -,
-CH.sub.2 O-(CH.sub.2 -CH.sub.2 O).sub.n,-C(=O)-CH.sub.2 -, and
-C(=O)-N(R')-(-CH.sub.2).sub.n,-CH.sub.2 -
wherein
n' is an integer from 1 to 3; and
R' is hydrogen or a C.sub.1 -C.sub.4 alkyl group;
t is an integer from 1 to 2;
Q is a polar organic group comprising N or P atoms as positive
charge carriers, and having the formula: ##STR20## wherein A.sup.+
is
i) a N or a P atom and R.sub.1, R.sub.2, and R.sub.3 are
independently an alkyl group having from 1 to 12 carbon atoms,
or
ii) a P atom and R.sub.1, R.sub.2, and R.sub.3 are independently an
alkyl group having from 1 to 12 carbon atoms, or an aryl group,
or
Q is ring selected from the group consisting of pyridine,
methylmorpholine, quinuclidine and alkylphosphacyclohexanes,
wherein an N or P atom in said ring is a positive charge carrier
bound to group L; and
X.sup.- is an anion.
11. A compound according to claim 10, wherein said anion is
selected from the group consisting of halogen, acetate, CH.sub.3
-Phenylene-SO.sub.3.sup.-, and R"-SO.sub.3.sup.-, wherein R" is
F-(CF.sub.2).sub.m, and m" is a integer from 1-4.
Description
The present invention relates to polishes for metal surfaces, based
on fluorinated polymers, waxes and organic solvents.
In the art there are known polishes based on said ingredients, in
the form of liquid emulsions and dispersions, or in paste.
Generally, such polishes are useful to impart to the substrates,
onto which they are applied, at least one of the following
properties:
- high and long-lasting gloss
- water-repellency
- resistance to soiling
- resistance to washings, also with detergents
- easy application.
Preparations of silicone-based polishes are described for example
in U.S. Pat. Nos. 4,273,584; 4,785,067 and 4,398,953.
Generally it is difficult to obtain, in a single polish, a good
combination of all the above-mentioned properties.
Japanese patent application 64-38480 describes
Compositions endowed with good characteristics of water-repellency
and resistance to soiling, and comprising, besides waxes and
silicone oils, a combination of low molecular weight
polytetrafluoroethylene and of perfluoropolyoxyalkylene.
It has now been found by the Applicant that the use of cationic
emulsifiers having perfluoropolyoxyalkylene structure improves the
aggregate characteristics of polishes based on dispersions of waxes
with fluorinated materials. In particular, such emulsifiers permit
to obtain polishes capable of imparting high gloss combined with
high water-repellency, resistance to soiling and to washings as
well as easy application and polishing to the substrates, onto
which they are applied.
In particular, the abovesaid emulsifiers possess a.
perfluoropolyoxyalkylene chain containing at least a cationic polar
group and have general formula
in which:
R is a chain of perfluorooxyalkylene units, having an average
molecular weight ranging from 400 to 2,000, but preferably from 500
to 1,000;
L is a divalent organic group preferably having one of the
following formulas:
t=1 or 2;
n=an integer from 1 to 3, extremes included;
R'=hydrogen, or an alkyl group having 1 to 4 carbon atoms;
Q is a polar organic group comprising N or P atoms as positive
charge carriers, and having the formula: ##STR1## A.sup.+ =a N or P
atom;
R.sub.1 R.sub.2 and R.sub.3, like or different from one another,
are alkyl groups containing from 1 to 12 carbon atoms, or, when
A.sup.+ is P, R.sub.1, R.sub.2, R.sub.3 can also be aryl groups; or
Q is an aromatic or aliphatic ring, either saturated or
unsaturated, containing N or P atoms as positive charge carrier
directly bound to group L, wherein such ring can optionally contain
alkyl substituents and other heteroatoms such as O and S. Examples
of such rings are given by pyridine, methylmorpholine, quinuclidine
and alkylphosphacyclohexanes.
X.sup.- =anion, preferably halogen, acetate or a group of
formula
or
R"=a group of formula F-(CF.sub.2).sub.m.sup.-
m=a number from 1 to 4, extremes included.
In such formula (I), perfluoropolyoxyalkylene chain R is composed
of perfluorooxyalkylene units statistically distributed along the
chain and having at least one of the following structures:
##STR2##
In particular, perfluoropolyoxyakylene chain R can have one of the
following structures: ##STR3## where Rf is an alkyl group C.sub.1
-C.sub.3, either thoroughly fluorinated or containing also an atom
of hydrogen or chlorine besides fluorine; R'f- is a -CF.sub.2 -
group or ##STR4## and m, n, p are such numbers as to impart to
CF.sub.3 R a molecular weight in the abovesaid range;
2) RfO(CF.sub.2 CF.sub.2 O).sub.n (CF.sub.2 O).sub.m R'f-
where, when t=1, Rf is -CF.sub.3, -C.sub.2 F.sub.5, while when t=2,
Rf is=R'f; R'f is a -CF.sub.2 - group; m, n have such values as to
satisfy the abovesaid molecular weight condition; ##STR5##
where Rf and R'f have the same significance as in the preceding
structure (1);
m, n, p, q are such numbers as to satisfy the abovesaid molecular
weight conditions; ##STR6##
where Rf i s -C.sub.3 F.sub.7 ; R'f is a ##STR7## and n has such a
value as to satisfy the abovesaid molecular weight conditions;
5) RfO(CF.sub.2 CF.sub.2 O).sub.n R'f- where Rf is -CF.sub.3,
-C.sub.2 F.sub.5 ; R'f is a -CF.sub.2 group, and n has such a value
as to satisfy the abovesaid molecular weight conditions;
6) RfO(CF.sub.2 CF.sub.2 CF.sub.2 O).sub.n R'f-
where Rf is -CF.sub.3, -C.sub.2 F.sub.5 ; R'f is a -CF.sub.2
CF.sub.2 - group, and n has such a value as to satisfy the
abovesaid molecular weight conditions.
Thus, it is an object of the present invention to provide polishes
for metal surfaces, based on dispersions, in organic solvents, of
waxes in combination with fluorinated materials selected from the
addition polymers of fluoroolefins such as tetrafluoroethylene,
chlorotrifluoroethylene and vinylidene fluoride, and the
perfluoropolyoxyalkylene oils, and combinations thereof, which
polishes contain at least an emulsifier of the cationic type,
comprised in the above-illustrated formula (I).
Preferred polishes according to the invention are the ones which
comprise, in per cent by weight:
- organic solvent: 50-90;
- waxes: 1-10;
- perfluoropolyoxyalkylene oil: 0.1-5 and preferably 0.5-3;
- polymer obtained from a fluoroolefin: 0.5-20 and preferably
1.5-20;
- cationic emulsifier of formula (I): 0.1-5.
Such polishes can also comprise from 0 to 10% by weight of
silicones, from 0 to 20% by weight of an aliphatic alcohol and from
0 to 20% by weight of an abrasive material.
In such compositions, the presence of silicones, in the abovesaid
ranges, is preferred when a more easily applicable polish is to be
obtained.
As solvents for the polishes of the invention it is possible to use
saturated and straight paraffin hydrocarbons containing from 9 to
12 carbon atoms; isoparaffins, such as for example the products
commercially known as Isopar (produced by Exxon Corp.); White
spirits, such as for example Shellsol (produced by Shell Co.) and
Exxsol (produced by Exxon Corp.); burning oil; terpenes such as for
example D-limonene; naphtha; aromatic hydrocarbons such as toluene,
xylene and the like, as well as volatile silicones, such as for
example cyclic silicones (cyclomethicones).
Utilizable waxes are, for example, vegetable waxes (carnauba wax,
rice wax, etc.), animal waxes (for example beeswax), mineral waxes
(ceresine, Montan wax), petroleum waxes (Hungarian paraffin) and
microcrystalline and synthetic waxes.
The perfluoropolyoxyalkylene oils which are contained in the
polishes of the invention are products known in the art. They are
compounds composed of chains comprising perfluoropolyoxyalkylene
units having at least one of the following structures: ##STR8##
In particular, such perfluoropolyoxyalkylenes exhibit an average
molecular weight ranging from 400 to 6,000, viscosities ranging
from 1 to 1,000 cSt, and preferably from 20 to 250 cSt, and they
belong to one or more of classes 1) to 6) described hereinbefore to
define chain R of the cationic emulsifiers of formula (I), with the
exception that in each of such classes Rf and R'f are
perfluoroalkyl groups either like or different from each other,
containing from 1 to 3 carbon atoms, depending on the class which
they belong to.
The perfluoropolyoxyalkylene oils of class (1) are commercially
known under the tradenames Fomblin.RTM. Y or Galden.RTM., while the
ones of class (2) are known under the tradename Fomblin.RTM. Z; all
said oils are produced by Montedison.
The perfluoropolyoxyalkylene oils of class (3) are prepared in
accordance with what is disclosed in U.S. Pat. No. 3,665,041; those
of class (4) are known under the tradename Krytox.RTM. and are
produced by Du Pont; those of class (5) are described in U.S. Pat.
No. 4,523,039 and in J. Am. Chem. Soc. 1985, 107, 1197-1201; those
of class (6) are described in European patent application No.
148,482.
Under the designation "fluoroolefin polymers", whenever used
herein, there are comprised both the homopolymers of the
above-mentioned monomers, and the copolymers of such monomers with
minor amounts of other fluorinated monomers, such as for example
hexafluoropropene, perfluoroalkylvinylethers and the like. The
abovesaid polymers have an average molecular weight ranging from
1,000 to 500,000. They can be prepared by any known method, such as
for example the polymerization of the gaseous monomers in an
aqueous medium or in solvents, or by irradiating, with .tau. rays
or with electron beams, polymers of higher molecular weight, or,
lastly, by thermal degradation of the latter.
Examples of utilizable fluoroolefin polymers are represented by the
commercial products Algoflon L.RTM. and Polymist.RTM. produced by
company Ausimont; AG Lube.RTM. produced by company Asahi Glass;
Vydax.RTM. and Teflon MP.RTM. produced by company Du Pont; Lubron
produced by company Daikin; Hostaflon Ceridust.RTM. produced by
company Hoechst; SST.RTM. produced by company Shambrock; Fluon.RTM.
and Whitcon TL.RTM. produced by company ICI, and in general by the
low molecular weight polymers utilized in inks and paints.
Among the silicones which are optionally utilizable in the polishes
of the invention, the following can be cited: polydialkylsiloxanes,
and preferably the polydimethylsiloxanes having a viscosity ranging
from 2 to 500 cSt, such as the products of the series Dow-Corning
200 Fluid; the organofunctional silicones, in particular the
aminofunctional silicones and the hydroxyfunctional silicones, and
the silicone resins in general.
Utilizable alcohols are the straight or branched aliphatic
alcohols, containing from 1 to 5 carbon atoms. Primary or secondary
alcohols containing 2 or 3 carbon atoms are preferably used.
Examples of abrasives are aluminium silicates, aluminium oxides,
kieselguhr.
A further object of the present invention are the compounds of
formula:
in which R, L, Q, X, t have the significance defined hereinbefore,
which are utilized as emulsifiers for the polishes of the
invention, as already mentioned herein.
Such compounds are preparable according to the following
methods:
1) When group L is a -CH.sub.20 -CO-CH.sub.2 -, the starting
material utilized is a perfluoropolyoxyalkylene of formula
R-CH.sub.2 OH, where R is a perfluoropolyoxyalkylene chain as
already defined herein for general formula (I). Such
perfluoropolyoxyalkylene is a product known in the art. It is
reacted by means of known esterification techniques with an acid of
formula XCH.sub.2 COOH, in which X is a halogen or a group of
formula (III) or (IV), thereby obtaining an ester of formula
##STR9##
Such ester is then subjected to quaternization reaction with a
tertiary base, such as a trialkylamine, or a trialkyl phoshine or
triaryl phosphine, or in an alcoholic solvent, so obtaining the
desired product in solution, or in a hydrocarbon solvent, wherefore
the product precipitates as a salt.
2) When group L is a -CH.sub.2 O(CH2CH.sub.2 O).sub.n CH.sub.2
CH.sub.2 - group, it is started from the compound RCH.sub.2
O(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CH.sub.2 OH (prepared by
ethoxylation, according to known methods, of
perfluoropolyoxyalkylene RCH.sub.2 OH with an ethylene oxide) by
reacting it with SOCl.sub.2 in order to obtain the compound
RCH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CH.sub.2 Cl which
is then quaternized with the previously mentioned tertiary
base.
3) When group L is a -CH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.n
COCH.sub.2 - group it is possible to operate as in the preceding
case (1), causing the esterification to occur with the XCH.sub.2
COOH acid of the ethoxylated compound of formula RCH.sub.2
(OCH.sub.2 CH.sub.2).sub.n OH (where R has the significance
indicated at point (1)) obtained by ethoxylation of
perfluoropolyoxyalkylene RCH.sub.2 OH with ethylene oxide in an
alkaline medium.
4) When group L is a -CO-NR' (CH.sub.2).sub.n -CH.sub.2 - group, it
is possible to start from an ester of formula RCOOCH.sub.3 -. Such
ester is a product known in the technique. It can be reacted
according to known techniques with a base of formula
HNR'-(CH.sub.2).sub.n -CH.sub.2 NR.sub.1 R.sub.2. Subsequently such
intermediate can be reacted with an alkylating agent such as, for
example, an alkyl halogenide, thereby obtaining the quaternization
of the aminic nitrogen atom contained therein.
An object of the present invention is to produce polishes, i.e.,
chemical compositions which can be applied very easily and are
utilizable for cleaning, polishing and protecting various
substrates. In particular, the polishes of the invention may be
utilized for cleaning, polishing and protecting painted or
unpainted metal surfaces of cars, airplanes, coaches and the like.
Such metal surfaces may be thus imparted with a high resistance to
water and to soiling, and provided with a high gloss and resistance
to washing with detergents. Further, such metal surfaces upon which
the polishes are utilized may be imparted with a protection against
corrosion.
The following examples are given to illustrate the present
invention and are not to be considered as a limitation thereof.
The polishes of the examples are prepared as follows.
In a glass vessel there are mixed the solvent and one or more waxes
in a fixed weight ratio, and heating is conducted until melting of
the wax.
Such mixture is introduced, while it is hot, into a second vessel,
which contains further solvent and (if it is utilized) a silicone
component, and which is kept under stirring.
The resulting mixture (base) is cooled to room temperature and then
the other ingredients are added thereto. Among these ingredients,
the perfluoropolyoxyalkylene oil is preferably added first,
maitaining the base under high-speed stirring (for example by means
of a Silverson laboratory stirrer), whereafter the cationic
emulsifier, either as such or in an alcohol solution, is added.
The anhydrous fluoroolefin polymer in the form of powder is then
added, and it is followed by a further silicone component (if it is
utilized) in an alcoholic solution. Lastly, if necessary, the
abrasive material is added.
An alternative method to the use of the fluoroolefin polymer in
powder is the method which utilizes a dispersion of the polymer in
a perfluoropolyosyalkylene oil among the ones cited hereinbefore,
or in a volatile chlorofluorocarbon, such as for example Freon.RTM.
or Delifrene.RTM.. In the former case, the amount of
perfluoropolyoxyalkylene oil utilized for such dispersion can
replace in whole or in part the initial addition of such oil. In
the latter-case, the chlorofluorocarbon can be evaporated from the
final composition.
When the addition of the various ingredients is completed, the
resulting composition is maintained under stirring for a few
minutes.
The polishes of the invention do not exhibit sedimentation of the
components even after months. Their stability in the time is
confirmed by their resistance to centrifugation, wherefore no
separation of the components takes place when the polishes are
subjected to centrifugation at 500 r.p. m. for 10 minutes.
Even if, operating at 1,000 r.p.m., a separation of the components
should occur after 10 minutes, it would be possible to obtain again
a homogeneous dispersion by means of a simple manual agitation.
The characteristics of the polishes according to the examples have
been determined by treating standard panels with constant amounts
of said polishes (0.7 g for each panel) either immediately after
application or after 1-10 washing cycles with a commercial shampoo
(Supershampoo Arexons) and subsequent drying.
The panel utilized for the test were painted with a paint for cars,
white or blue (depending on the test), and had the following
dimensions: 30.times.30 cm. The white panels were used for
water-repellency and resistance to carbon black adhesion tests,
while the blue panels were utilized for gloss measurements.
In order to permit a direct comparison between a treated panel and
an untreated panel, each panel was divided into two identical parts
by means of an adhesive masking tape, so that the untreated part
was utilized as a check.
For each type of test, a new clean panel was washed with
Supershampoo Arexons, was rinsed with water and was dried. The
polish to be tested was applied onto the panel by means of a clean
piece of cotton wool and was let completely dry in 10 minutes.
The characteristics of easy application and rub out after drying
were subjectively determined on the basis of the comparison between
conventional polishes and fluorinated polishes.
The water-repellency characteristics were defined by the time, in
seconds, necessary for a water jet to flow away from the panel
sloping at 30.degree..
In such tests, operating with high-quality non-fluorinated polishes
of the commercial type, times of 10 seconds are generally
determined, while times of less than 5 seconds are considered as
good and times of 1-2 seconds are considered as excellent (U.S.
Pat. No. 4,273,584).
The resistance-to-soiling characteristics were determined by
applying carbon black powder onto the treated surface of the panel
and by heating the panel to 70.degree. C. for 3 hours.
Then the panel was shaken to remove the powder excess, and a piece
of soft paper was passed over the panel, whereafter the resistance
to soiling was evaluated as follows:
- excellent, when the carbon black powder could be easily removed
without ex erring any pressure;
- good, when the powder could be removed by exerting only a slight
pressure on the surface;
- fair, when it was necessary to exert a higher pressure on the
surface;
- poor, when a permanent grey halo remained on the surface even
exerting a strong pressure.
The cycle was then repeated on the same treated panel, after
washings with shampoo for cars.
Repeated cyclic thermal treatments with carbon black on the same
panel represent extremely drastic conditions.
The gloss characteristics were determined by means of a Micro Tri
Gloss glossmeter produced by Byk Gardner.
The panel gloss values reported in the examples are the average of
nine measurements carried out near the corners and in the middle of
the panel. For this determination, blue-painted panels were
utilized, operating at an angle of 20.degree.. The untreated
surfaces of the panel were compared after application and rub out
of the polishes also after ten washings with Supershampoo
Arexons.
EXAMPLE 1
Preparation of polish 1A (comparative)
In a suitable vessel, 2.93 g of carnauba wax, 1.46 g of ceresine
and 8.78 g of white spirit were mixed.
The mixture was heated until melting of the waxes.
In a second vessel, 0.8 g of silicone oil DC 200/20.RTM. produced
by Dow Corning ) were mixed with 59.98 g of white spirit
Shellsol.RTM. (produced by Shell); the mixture was stirred by means
of a high-speed Silverson.RTM. stirrer, whereafter the hot mixture
of waxes in white spirit, previously prepared, was added
thereto.
The resulting mixture (base (I)) was then additioned, at room
temperature and under stirring, with 0.25 g of silicone resin Z
6018.RTM. (produced by Dow Corning) dissolved in 0.75 g of
isopropyl alcohol, and then, in the order, with 15.05 g of
isopropyl alcohol and with 10 g of Sillitin N.RTM. (abrasive). The
dispersion was then maintained under stirring until complete
incorporation of the abrasive. It exhibited the following
composition, expressed in per cent by weight:
______________________________________ Carnauba wax 2.93 Ceresine
1.46 White spirit 68.76 Silicone oil DC 200/20 0.8 Silicone resin Z
6018 0.25 Isopropyl alcohol 15.80 Sillitin N 10.0
______________________________________
Preparation of polish 1B (comparative)
73.95 g of basic composition (I) prepared for polish 1A were
additioned, at room temperature and under stirring, with 1.5 g of
perfluoropolyoxyalkylene oil of class (1) (Fomblin Y04) having a
viscosity of 40 cSt, and then, in the order, with 3.31 g of
tetrafluoroethylene/hexafluoropropene copolymer having an average
molecular weight equal to 350,000 (prepared by treating with .tau.
rays of 12.5 MRad a higher molecular weight copolymer), with 0.25 g
of silicone resin Z 6018 dissolved in 0.75 g of isopropanol, with
10.24 g of isopropanol and, lastly, with 10 g of Sillitin N
(abrasive).
The mixture was maintained under stirring until complete
incorporation of the abrasive. The mixture had the following
composition expressed in per cent by weight:
______________________________________ Carnauba wax 2.93 Ceresine
1.46 White spirit 68.76 DC 200/20 0.8 Silicone resin Z 6018 1.25
Isopropanol 10.99 Sillitin N 10.0 Fomblin Y04 1.5
Tetrafluoroethylene copolymer 3.31
______________________________________
Preparation of polish 1C (according to the invention)
In this preparation, a cationic emulsifier was utilized, which
exhibited the formula:
in which:
Pi=pyridine;
R=perfluoropolyoxyalkylene chain having the structure of class (1)
and an average molecular weight=700; n=1.5.
73.95 g of base (I) prepared for polish 1A were additioned, under
stirring, with 1.5 g of the same perfluoropolyoxyalkylene oil
utilized for polish 1B, and then, in the order, with 0.77 g of the
above-described cationic emulsifier, dissolved in 9.47 g of
isopropanol, then with 3.31 g of the tetrafluoroethylene copolymer
utilized for polish 1B, with 0.25 g of silicone resin Z 6018
dissolved in 0.75 g of isopropanol, and lastly with 10 g of
abrasive Sillitin N, maintaining the resulting mixture under
stirring until complete incorporation of the abrasive.
The resulting dispersion had the following composition, expressed
in per cent by weight:
______________________________________ Carnauba wax 2.93 Ceresine
1.46 White spirit 68.76 Silicone oil DC 200/20 0.8 Silicone resin Z
6018 1.25 Isopropanol 10.22 Sillitin N 10.00 Fomblin Y04 1.5
Tetrafluoroethylene copolymer 3.31 Cationic emulsifier 0.77
______________________________________
Preparation of polish 1D (according to the invention)
It was operated as is described for polish 1C, with the only
exception that the cationic emulsifier utilized had the
formula:
where:
R has the same significance as in the cationic emulsifier utilized
in polish 1C,
n=1.5.
Preparation of polish 1E (comparative)
It was operated as is described for polish 1C, with the only
exception that instead of the cationic emulsifier, there was used
an equal amount by weight of a fluorinated cationic emulsifier of
formula:
wherein R has the same significance as in the cationic emulsifier
utilized in polish 1C.
The present emulsifier can be considered as a mixture of a
fluorinated cationic emulsifier with a non-fluorinated hydrocarbon
cationic emulsifier.
Preparation of polish 1F (comparative)
73.95 g of base (I) obtained in the preparation 1A were additioned,
under stirring, with 0.77 g of the cationic emulsifier of
preparation 1C, dissolved in 14.28 g of isopropanol, and then, in
the order, with 0.25 g of silicone resin Z 6018 dissolved in 0.75 g
of isopropanol, and with 10 g of Sillitin N, maintaining the
mixture under stirring until total incorporation of the
abrasive.
The resulting polish differs from polishes 1C and 1D for the
absence of the tetrafluoroethylene copolymer and of the
perfluoropolyoxyalkylene oil, and furthermore, with respect to
polish 1E, for the presence of the cationic emulsifier, instead of
the anionic emulsifier.
With respect to polish 1A, it differs only for isopropanol content
(15.03% instead of 15.8%) and for the presence of the cationic
emulsifier.
The characteristics of the polishes of the present example are
reported in the following Table I.
TABLE I
__________________________________________________________________________
Composition 1A 1B 1C 1D 1E 1F
__________________________________________________________________________
Water-repellency just after treatment excellent excellent excellent
excellent excellent good after 1 washing good good excellent
excellent good good after 3 washings good good good good good poor
after 5 washings poor good good good fairly good poor after 10
washings poor poor fair good good fair good poor Gloss at
20.degree. before treatment 29,6 33,3 38,2 42,1 33,4 33,3
immediately after treatment 55,2 56,2 57,5 60,4 56,4 55,0 Gloss
retention (*) 86,5 68,9 50,5 43,5 69 65,2 before/after treatment
(%) after 1 washing 55,6 58,4 59,5 63,2 58,9 55,4 after 3 washings
55,1 59,1 59,3 63,5 59,6 55,4 after 5 washings 56,0 59,0 59,6 64,2
60 56,2 after 10 washings 57,7 59,5 59,3 64,6 60,2 58,2 Gloss
retention (**) 91 87,4 91,5 81,3 85,8 87,1 before/after 10 washings
(%) Resistance to soiling (carbon black test) immediately after
treatment poor poor excellent excellent good fair good after 1
washing excellent excellent fair good fair good after 3 washings
good good poor poor after 5 washings fair good good after 10
washings poor poor
__________________________________________________________________________
(*) Retention % = gloss after treatment initial gloss/initial gloss
(**) Retention % = gloss after treatment initial gloss/gloss after
10 washings initial gloss
EXAMPLE 2
Preparation of polish 2A (comparative)
73.3 g of base (I) utilized in polish 1A were additioned, under
stirring, with 1.52 g of the same perfluoropolyoxyalkylene oil
(Fomblin YO4) used for polish 1B, and then, in the order, with 0.78
g of a commercial cationic emulsifier, as defined hereinafter,
dispersed in 11.8 g of isopropanol, then with 2.5 g of the same
tetrafluoroethylene/hexafluoropropene copolymer used in polish 1B,
and lastly with 10.1 g of Sillitin N, and the mixture was stirred
until total incorporation of the abrasive.
The cationic emulsifier used herein is a quaternary alkyl ammonium
salt bound through a non-fluorinated organic group to a
perfluoroalkyl chain CF.sub.3 (CF.sub.2).sub.a.sup.-. Such
emulsifier is marketed under the designation Forofac 1179 by
Atochem and it can be commonly utilized as an emulsifier both in
the solid form and in alcoholic solution (or dispersion).
The dispersion so prepared exhibits the following composition in
per cent by weight:
______________________________________ Carnauba wax 2.9 Ceresine
1.44 White spirit 66.16 Silicone oil DC 200/20 0.8 Isopropanol
11.80 Sillitin N 10.10 Fomblin Y04 1.52 Tetrafluoroethylene
copolymer 2.50 Cationic emulsifier 0.78
______________________________________
Preparation of polish 2B (comparative)
The preceding preparation 2A was repeated, with the only exception
that a different cationic emulsifier, marketed under the trade
designation Surflon S-121, produced by Asahi Glass Co., was used.
Said emulsifier is a quaternary ammonium salt bound, through a
non-fluorinated organic group, to a perfluoroalkyl chain CF.sub.3
(CF.sub.2).sub.n -.
Preparation of polish 2C (comparative)
Preparation 2A was repeated with the only exception that, as an
emulsifier, an anionic emulsifier of formula:
was utilized, wherein R is a perfluoropolyoxyalkylene chain similar
to the one existing in the cationic emulsifier of polish 1C.
Preparation of polish 2D (comparative)
Preparation 2A was repeated with the only exception that an anionic
emulsifier of formula:
was utilized, wherein R is a perfluoropolyoxyalkylene chain similar
to the one of the cationic emulsifier of polish 1C.
Preparation of polish 2E (according to the invention)
Preparation 2A was repeated with the exception that she utilized
emulsifier was a cationic emulsifier analogous with the one used in
polish 1C.
The characteristics of the polishes so prepared are reported in the
following Table II.
TABLE II
__________________________________________________________________________
Composition 2A 2B 2C 2D 2E
__________________________________________________________________________
Water-repellency just after treatment excellent excellent excellent
excellent excellent after 1 washing good excellent excellent good
excellent after 3 washings fairly good good good good good after 5
washings fair good good good good good after 10 washings fair good
poor fair good fair good fair good Gloss at 20.degree. before
treatment 34,3 36,8 41,7 38,7 42,9 after treatment 55,5 49,8 55,2
49,7 59,8 gloss retention 61,8 35,3 32,3 28,4 39,4 before/after
treatment (%) after 1 washing 56,5 49,2 56,2 50,7 59,6 after 3
washings 56,7 50,7 56,5 52,9 60,0 after 5 washings 57,3 51,7 57,6
52,6 60,3 after 10 washings 57,1 50,9 57,7 52,9 60,9 gloss
retention 93 92,2 84,4 77,5 94 after treatment/after 10 washings
(%) Resistance to soiling (test with carbon black) immediately
after treatment poor poor poor poor good
__________________________________________________________________________
EXAMPLE 3
In this example, the characteristics of polishes according to the
invention and not according to the invention, having different
fluorinated component contents are compared.
Preparation of polish 3A (according to the invention)
Preparation 1C was repeated with the exceptions that the cationic
emulsifier content was increased from 0.77% to 1.5% and that the
isopropanol content was correspondingly reduced from 10.22% to
9.49%, the amount of the remaining components being identical in
both polishes.
Preparation of polish 3B (according to the invention)
Preparation 1C was repeated, but varying the amounts of the
components in order to have the following per cent composition:
______________________________________ Carnauba wax 1.47 Ceresine
0.73 White spirit 68.76 Silicone oil DC 200/20 0.8 Silicone resin Z
6018 0.25 Isopropanol 8.83 Sillitin N 10.0 Fomblin Y 04 3.0
Tetrafluoroethylene copolymer 4.62 Cationic emulsifier 1.54
______________________________________
In the following Table III, the characteristics of polishes 3A and
3B are compared with the characteristics of polishes 1C and 1B.
TABLE III
__________________________________________________________________________
Composition 1B 1C 3A 3B
__________________________________________________________________________
Water-repellency just after treatment excellent excellent excellent
excellent after 1 washing good excellent excellent excellent after
3 washing good good good excellent after 5 washing good good good
excellent after 10 washing poor fairly good good excellent Gloss at
20.degree. before treatment 33,3 38,2 40 35,1 after treatment 56,2
57,5 56 61,3 gloss retention 68,9 50,5 40 74,6 before/after
treatment (%) after 1 washing 58,4 59,5 59,2 66,1 after 3 washings
59,1 59,3 58,7 65,8 after 5 washings 59,0 59,6 59,1 66,1 after 10
washings 59,5 59,3 59,9 66,3 gloss retention 87,4 91,5 80,4 84
after treatment/after 10 washings (%) Resistance to soiling (test
with carbon blanck) immedyately after treatment poor excellent
excellent excellent after 1 washing excellent excellent excellent
after 3 washings good good good after 5 washings fair good good
good
__________________________________________________________________________
* * * * *